Composite material

ABSTRACT

A composite material comprising a first layer which comprises a surfactant component, surfactant-generated microcells, a gel catalyst component and a binder component, and a second layer which comprises a metallic component is provided. The first layer may further comprise a filler component. In addition, the composite material may further comprise a substrate to which the first layer is adhered. The composite materials have heat insulating and fire resistant characteristics and are particularly suited for use in building materials and mattresses.

[0001] Application Ser. No. 10/354,219, which claims priority under 35U.S.C. §119(e) to Provisional Application No. 60/352,693; of pendingU.S. application Ser. No. 09/663,255 filed on Sep. 15, 2000, whichclaims priority under 35 U.S.C. §119(e) to Provisional Application No.60/168,057, filed on Nov. 30, 1999; and of pending U.S. application Ser.No. 09/955,395 filed on Sep. 18, 2001.

FIELD OF THE INVENTION

[0002] This invention relates to composite materials which may be usedin building materials, motor vehicles, heaters, dryers, fire resistantclothing, mattresses, draperies, furniture upholstery and the like. Theinvention further relates to articles of manufacture that utilize thecomposite materials of the invention.

BACKGROUND OF THE INVENTION

[0003] Various attempts have been made to produce heat insulating fireresistant structural materials and fabrics having characteristics thatmake them suitable for use in building materials, clothing, motorvehicles, mattresses and in other applications.

[0004] U.S. Pat. No. 5,540,980 is directed to a fire resistant fabricuseful for mattress ticking. The fabric is formed from a corespun yarncomprising a high temperature resistant continuous filament fiberglasscore and a low temperature resistant staple fiber sheath, whichsurrounds the core. The fiberglass core comprises about 20% to 40% ofthe total weight of the corespun yarn while the sheath comprises about80% to about 60% of the total weight of the corespun yarn. The corespunyarn can be woven or knit to form fabric with fire resistantcharacteristics. When exposed to a flame, the sheath chars and thefiberglass core serves as a fire barrier. In a preferred embodiment, thesheath is made from cotton.

[0005] U.S. Pat. No. 5,091,243 discloses a fire barrier fabriccomprising a substrate formed of corespun yarns and a coating carried byone surface of the substrate. Other fire resistant fabrics includeFenix™ (Milliken, LaGrange, Ga.) and fabrics made by Freudenberg(Lowell, Mass.), Ventex Inc. (Great Falls, Va.), BASF, Basofil FiberDivision (Enka, N.C), Carpenter Co. (Richmond, Va.), Legget and Platt(Nashville, Tenn.), Chiquala Industries Products Group (Kingspoint,Tenn.), and Sandel (Amsterdam, N.Y). DuPont also manufacturers a fabricmade from Kevlar™ thread. In addition, the mattress industry hasattempted to manufacture mattresses by using Kevlar™ thread, glassthread, flame retardant polyurethane foams, flame retardant ticking,flame retardant cotton cushioning and flame retardant tape. However, useof these materials adds to the cost of mattresses and may result in acost-prohibitive product. Additionally, some fire-resistant threads,such as glass threads, are difficult to work with and can break, addingto the time required for manufacturing the mattress, which alsotranslates into added costs.

[0006] Flame retardant tapes are also difficult to work with andincrease production time. In addition, flame retardant tapes are onlyavailable in a limited number of colors and sizes. Flame retardantpolyurethanes may release noxious gases when they smolder and ignite.Furthermore, the process for flame retarding ticking often compromisesthe desired characteristics of the ticking (e.g. it may no longer besoft, drapable, pliable, flexible, etc).

[0007] For many years substrates such as fiberglass have been coatedwith various compositions to produce materials having utility in, amongother applications, the building industry. U.S. Pat. No. 5,001,005relates to structural laminates made with facing sheets. The laminatesdescribed in that patent include thermosetting plastic foam and haveplanar facing sheets comprising 60% to 90% by weight glass fibers(exclusive of glass micro-fibers), 10% to 40% by weight non-glass fillermaterial and 1% to 30% by weight non-asphaltic binder material. Thefiller materials are indicated as being clay, mica, talc, limestone(calcium carbonate), gypsum (calcium sulfate), aluminum trihydrate(ATH), antimony trioxide, cellulose fibers, plastic polymer fibers or acombination of any two or more of those substances. The patent furthernotes that the filler materials are bonded to the glass fibers usingbinders such as urea-, phenol- or melamine-formaldehyde resins (UF, PF,and MF resins), or a modified acrylic or polyester resin. Ordinarypolymer latexes used according to the disclosure areStyrene-Butadiene-Rubber (SBR), Ethylene-Vinyl-Chloride (EVCl),PolyVinylidene Chloride (PvdC), modified PolyVinyl Chloride (PVC),PolyVinyl Alcohol (PVOH), and PolyVinyl Acetate (PVA). The glass fibers,non-glass filler material and non-asphaltic binder are all mixedtogether to form the facer sheets.

[0008] U.S. Pat. No. 4,745,032 discloses an acrylic coating comprised ofone acrylic underlying resin, which includes fly ash and an overlyingacrylic resin, which differs from the underlying resin.

[0009] U.S. Pat. No. 4,229,329 discloses a fire retardant coatingcomposition comprising fly ash and vinyl acrylic polymer emulsion. Thefly ash is 24 to 50% of the composition. The composition may alsopreferably contain one or more of a dispersant, a defoamer, aplasticizer, a thickener, a drying agent, a preservative, a fungicideand an ingredient to control the pH of the composition and therebyinhibit corrosion of any metal surface to which the composition isapplied.

[0010] U.S. Pat. No. 4,784,897 discloses a cover layer material on abasis of a matting or fabric, which is especially for the production ofgypsum boards and polyurethane hard foam boards. The cover layermaterial has a coating on one side, which comprises 70% to 94% powderedinorganic material, such as calcium carbonate, and 6% to 30% binder. Inaddition, thickening agents and cross-linking agents are added and ahigh-density matting is used.

[0011] U.S. Pat. No. 4,495,238 discloses a fire resistant thermalinsulating composite structure comprised of a mixture of from about 50%to 94% by weight of inorganic microfibers, particularly glass, and about50% to 6% by weight of heat resistant binding agent.

[0012] U.S. Pat. No. 5,965,257, issued to the present assignee, theentire disclosure of which is incorporated herein by reference,discloses a structural article having a coating which includes only twomajor constituents, while eliminating the need for viscosity modifiers,for stabilizers or for blowing. The structural article of U.S. Pat. No.5,965,257 is made by coating a substrate having an ionic charge with acoating having essentially the same iconic charge. The coating consistsessentially of a filler material and a binder material. The assignee,Elk Corporation of Dallas, produces a product in accordance with theinvention of U.S. Pat. No. 5,965,257 which is marketed as VersaShield®.

[0013] As indicated in U.S. Pat. No. 5,965,257, VersaShield® has avariety of uses. However, it has been found that the products made inaccordance with U.S. Pat. No. 5,965,257 are not satisfactory for certainuses because they lack sufficient drapability.

[0014] U.S. patent application Ser. No. 09/955,395, filed on Sep. 18,2001, also assigned to the present assignee, the entire disclosure ofwhich is incorporated herein by reference, addresses these inadequacieswith a fire resistant fabric material comprising a substrate having anionic charge coated with a coating having essentially the same ioniccharge wherein the coating comprises a filler component which includesclay and a binder component. The fire resistant fabric material thusproduced has satisfactory flexibility, pliability and drapabilitycharacteristics. However, while this material is suitable as a fireresistant fabric material, it is desirable to provide a fire resistantmaterial that would also have cushioning or “bounce back”characteristics.

[0015] U.S. Pat. No. 6,228,497 teaches a fire resistant glass fiberwhich is made by mixing together glass fibers, a binder and calciumcarbonate. In addition, clay may be added to improve fire resistance.

[0016] U.S. Pat. No. 4,994,317 teaches a multilayered fire resistantmaterial which comprises a flame durable textile fabric substrate, aflexible silicone polymer layer, and a heat reflective paint. Clay maybe added to the silicone layer to enhance flame resistance.

[0017] GB 2167060 teaches a fire resistant material comprising syntheticmineral fibers (including glass wool), clay and a binder. The fireresistant material is made by combining the components. The binder ispreferably starch or modified starch; condensates of phenol, urea,melamine, resorcinol, tannin with aldehyde, isocyanates, reactivecements; binders formed in situ by inter-reaction between silica andcalcium; hydraulic cements; and potassium and sodium silicates.

[0018] U.S. patent application Ser. No. 10/354,216, filed on Jan. 29,2003, which this application claims priority to as acontinuation-in-part, relates to fire resistant structural materials andto fire resistant fabric materials made therefrom. The structuralmaterials comprise a surfactant component, surfactant generatedmicrocells, a filler component and a binder component. The structuralmaterial is fire resistant. The structural material may be used to coata substrate to make fire resistant fabric materials.

[0019] U.S. patent application Ser. No. 10/354,220, filed on Jan. 29,2003, which this application claims priority to as acontinuation-in-part, relates to a structural material comprising aprefabricated microcell component, a surfactant component, asurfactant-generated microcell component, a filler component and abinder component. The prefabricated microcell component is essentially ahollow sphere or a component capable of forming a hollow sphere that hasbeen constructed or manufactured before being employed in the structuralmaterial. The structural material may be used to coat a substrate tomake a fire resistant fabric material.

[0020] U.S. patent application Ser. No. 10/354,219, filed on Jan. 29,2003, which this application claims priority to as acontinuation-in-part, relates to a structural material comprising asurfactant component, surfactant-generated microcells, a gel catalystcomponent and a binder component. The structural material may furthercomprise a filler component. The structural material may be used to coata substrate to make a fire resistant fabric material.

[0021] However, while these materials may be suitable as fire resistantfabric materials, it is desirable to provide a fire resistant materialthat would also have cushioning or “bounce back” characteristics andhave heat-insulating properties.

SUMMARY OF THE INVENTION

[0022] The present invention relates to a composite material comprisinga first layer which comprises a surfactant component,surfactant-generated microcells, a gel catalyst component and a bindercomponent, and a second layer which comprises a metallic component. Thecomposite material may further comprise a filler component. Thecomposite material has heating insulating and fire resistancecharacteristics. In addition, the composite material may also comprise asubstrate to which the first layer is adhered to provide a coatedsubstrate. The substrate may be planar and the first layer may beadhered to one or both sides of the substrate. The second layer may beadhered to one or both first layer surfaces or to the substratedirectly. If no substrate is employed and if the first layer is planar,then the second layer may be adhered to one or both sides of the firstlayer. Moreover, the composite material may further include a waterrepellent material, an antifungal material, an antibacterial material, asurface friction agent, a flame retardant material and/or an algaecide.Further, the composite material may be colored with dye.

[0023] The composite materials of the present invention may be employedin building materials to make heat insulating, fire resistant buildingmaterials. In such an embodiment, the composite materials of the presentinvention may be used to coat building materials, such as gypsum boardsand siding materials, including sheathing. The building materials may beprepared during the building material making process to include thecomposite materials of the present invention or the composite materialsmay be utilized after the building materials have already beeninstalled. The binder is preferably acrylic latex. The surfactant may beany surfactant capable of forming microcells. In a preferred embodiment,the surfactant is a fast soap, such as ammonium lauryl sulfate (ALS). Afast soap generates microcells quickly in quantity and/or volume. Whenthe composite material comprises filler, the filler is preferably clay.

[0024] In a particularly preferred embodiment, the first layer of thecomposite material does not bleed through the substrate during thematerial making process. The substrate may be any suitable reinforcementmaterial capable of withstanding processing temperatures and ispreferably woven fiberglass.

[0025] The composite material of the present invention may be used as astandalone product, for example, as a foam material, or it may also beused in conjunction with (e.g. as a liner for) a building material, orit may be applied to attic ceilings, or it may be used with a decorativefabric which may itself be fire resistant.

DETAILED DESCRIPTION

[0026] The composite material of the invention comprises a first layerwhich comprises a surfactant component, surfactant-generated microcells,a gel catalyst component and a binder component, and a second layerwhich comprises a metallic component. The structural material mayfurther comprise a filler component. As used herein,surfactant-generated microcells are essentially voids or hollow sphereswhich are formed by the presence of a surfactant during the fireresistant material making process. The surfactant component of thepresent invention is capable of forming such microcells. Thesurfactant-generated microcells impart various characteristics to thecomposite materials of the present invention, including, inter alia,improved fire resistance, flexibility, pliability, drapability, and“bounce back”. The gel catalyst component may further enhance any andall of these characteristics. The metallic component imparts heatinsulating properties to the structural material and may be selectedfrom the group consisting of aluminum and stainless steel. The metalliccomponent may be a metal film or foil, or it may be sprayed onto thefirst layer or onto the substrate and then heat dried in an oven. In apreferred embodiment, the metallic component is aluminum foil.

[0027] In accordance with the invention, a composite material may bemade by adhering the first layer to one or both sides of a substrate toprovide a coated substrate. The second layer is adhered to the firstlayer. In a preferred embodiment, the first layer does not bleed throughthe substrate during the material making process.

[0028] The composite materials of the present invention are prepared bypreparing the first layer by using a binder component such as a highperformance heat-reactive acrylic latex polymer and/or a non-heatreactive styrene butadiene latex to bond the filler materials together.Where the first layer of the composite material is adhered to asubstrate, the binder component may act also to bond the first layer tothe substrate. In one embodiment of the invention, the binder componentis Rhoplex 3349 (available from Rohm and Haas, Philadelphia, Pa.) and/orRovene 4402 (Mallard Creek Polymers, Charlotte, N.C.). Additional oralternative binders include, inter alia, Hycar™ 26469, Hycar™ 26472,Hycar™ 26484, Hycar™ 26497, Hycar™ 264552, Hycar™ 264512, Hycar™ 264582,Hycar™ 26083 (low formaldehyde), Hycar™ 9201 (low formaldehyde), Hycar™1552 (nitrile), Hycar™ 1571 (nitrile), Vycar™ 552, Hycar™ 2679 acryliclatex polymer (all Hycar™ and Vycar™ products are supplied by B. F.Goodrich Company of Cleveland, Ohio. Binder components may also includeCymel™ 373 (available from American Cyanamid), RHOPLEX™ TR 407 and R&HGL-618 latex both available from Rohm & Haas, and Borden FG-413F UFresin (available from Borden). It is believed, however, that any linearpolymer, linear copolymer or branched polymer may be useful in preparingthe first layer, such as those available from BASF and Goodyear Furtherpossible binder materials include butyl rubber latex, SBR latex,neoprene latex, polyvinyl alcohol emulsion, SBS latex, water basedpolyurethane emulsions and elastomers, vinyl chloride copolymers,nitrile rubbers and polyvinyl acetate copolymers. In a preferredembodiment, an SBR latex is used. SBR latex adds good softnesscharacteristics but is not a flame retardant. To improve fireresistance, an acrylic latex may be added or substituted. The moreacrylic latex, the better the fire resistance of the material. However,softness is decreased when acrylic latex is substituted for SBR latex.In a particularly preferred embodiment, the binder component comprisesRhoplex 3349 and Rovene 4402.

[0029] The surfactant component of the present invention may be anysurfactant capable of forming microcells during the making of the firstlayer In a preferred embodiment, the surfactant component comprises afast soap, such as ammonium lauryl sulfate (ALS) (e.g. Stepanol AM;Stepan Chemicals, Northfield, Ill.) and sodium lauryl sulfate (SLS).Generally, a “fast soap” is a soap which is capable of efficientlymodifying the surface tension of a solvent, such as water. However,other surfactants may also be used which are not characterized as fastsoaps but which are capable of forming microcells. Fast soaps, such asALS, form microcells that are resilient and are generally stable to theheat of processing. Surfactant-generated microcells are generally notstable at temperatures above 350° F. Additional components may be addedto further stabilize the microcells, as further discussed below.However, if so desired, a surfactant which forms “weak” microcells maybe used. The “weak” microcells may burst during processing to producecollapsed microcells which produce a less flexible composite material.

[0030] The gel catalyst component of the present invention may be anycomponent known in the art which is capable of catalyzing gel formation.In a preferred embodiment, the gel catalyst is SSF-GEL available fromParachem (Dalton, Ga.). In addition, other catalysts may be added topromote vulcanization to provide permanent cross-linking and tothermoset the first layer which can enhance the strength of thesurfactant-generated microcell structure. In a preferred embodiment ofthe present invention, UP-750 (a sulfur catalyst available from Tiarco,Dalton, Ga.) is such a catalyst. In addition, Octocure®-590,Octocure®-456 and Octocure®-462 (available from Tiarco, Dalton, Ga.) mayalso be used for this purpose.

[0031] The gel catalyst may catalyze gel formation very quickly. Inorder to control gel formation catalyzation, very small amounts of gelcatalyst may be added by, for example, diluting the gel catalyst andadding a small volume of diluted gel catalyst. Since gel formation mayoccur very quickly upon addition of gel catalyst, the binder componentand surfactant component may be mixed together first andsurfactant-generated microcells may be introduced to that mixture by anymethod known in the art, such as by using a roamer, then the gelcatalyst may be added in order to ensure gel formation does not occurprior to surfactant-generated microcell formation.

[0032] As noted, surfactant-generated microcells may be created by anymeans known in the art, such as, but not limited to, blowing air intothe mixture, agitation or by a foamer. Surfactant-generated microcellsmay also be introduced using chemical blowing agents, such as azocompounds which release nitrogen gas.

[0033] In one embodiment of the present invention, the first layer ofthe composite material is made by combining the binder component, thesurfactant component and the filler component together and creatingsurfactant-generated microcells. Surfactant-generated microcells may becreated by any means known in the art, such as, but not limited to,blowing air into the mixture, agitation or by a foamer.Surfactant-generated microcells may also be introduced using chemicalblowing agents, such as azo compounds which release nitrogen.

[0034] In one embodiment of the invention, the binder/surfactant mixtureis subjected to a roamer. The foamer acts to inject air into the mixtureso that the surfactant forms microcells within the mixture. The foamermay comprise a tube-like component having a multitude of pins which arecapable of rotating in opposing directions (e.g. some pins moveclockwise and some move counterclockwise). The mixture of binder andsurfactant is added to the foamer through a port on one side and, as itpasses through the foamer, the pins rotate causing the introduction ofair and the creation of surfactant-generated microcells. Additional airmay also be introduced into the roamer at another port to furtherenhance surfactant-generated microcell formation. Aftersurfactant-microcell generation, the gel catalyst may be added through aport of the foamer. The mixture may then be spread onto a substrate,such as a fiberglass mat. Alternatively, if no substrate is desired, themixture may be spread onto a receiving platform, such as a steel tray toform a free-standing sheet. Whether applied to a substrate or areceiving platform, the material is then subjected to heat in an oven.Processing temperatures are preferably between about 280° F. to about350° F. The heat of processing further enhances gel formation by causingthe reaction to occur at a faster rate.

[0035] In a preferred embodiment, the surfactant-generated microcellsare stable to the heat of processing. As noted, generallysurfactant-generated micrcocells are not stable at temperatures above350° F. The filler is added to the mixture together with the surfactantand binder and before the addition of the gel catalyst. Preferably, thesurfactant-generated microcells are relatively small and uniform insize.

[0036] In another embodiment, the first layer of the composite materialalso includes a surfactant capable of regulating surfactant-generatedmicrocell formation which is added prior to the addition of the gelcatalyst. One such surfactant is Stanfex 320, (Parachem, Dalton, Ga.).The surfactant capable of regulating surfactant-generated microcellformation can ensure that the microcells remain within a preferred sizerange (e.g. do not get too big) and form in a relatively monodispersestate (i.e., are of the same general size). In a preferred embodiment,the surfactant-generated microcells are about 5.0 μ to about 20.0 μ indiameter. In addition, citric acid may be used to ensure that thesurfactant-generated microcells are spread out uniformly.

[0037] It may also be desirable for the first layer of the compositematerials to include a dispersant which acts to keep the mixturecomprising the binder, surfactant and gel catalyst well dispersed duringthe material making process. Examples of such dispersants include, interalia, TSPP, Accuma 9300, Accuma 9400 and Accuma 9000 (all available fromRohm & Haas).

[0038] The second layer comprising the metallic component may be adheredto the first layer by any means known in the art. In a preferredembodiment, the metallic component is aluminum foil and is applied tothe first layer while the first layer is still wet. When the material issubjected to the heat of an oven to dry the first layer, an adhesivebond is formed between the dried first layer and the aluminum foil.Alternatively, the metallic component may be adhered by electrodeposition, spraying, knife coating, or any other means known in theart.

[0039] The composite materials of the present invention are flexible,pliable and have good drapability characteristics. In addition they aredurable and preferably do not crack upon bending. Durability of thecomposite material may be enhanced by adding components capable ofstabilizing the surfactant-generated microcells. Such components includesurfactants such as ammonium stearate (Parachem, Dalton, Ga.), octosolA18 (Tiarco Chemicals, Dalton, Ga.), A-1 (disodiumn-alkylsulfosuccinate; Tiarco Chemicals), 449 (potassium oleate, TiarcoChemicals), and Stanfex 320. The surfactant-generated microcell may bestabilized by making the wall of the microcell thicker. A surfactantwhich comprises a long waxy chain may be particularly useful forstabilizing the microcells.

[0040] The first layer of the composite material may further include across-linking component, such as melamine (Borden Chemicals, Morganton,N.C.) and/or ammonium chloride. The cross-linking component is useful toimprove durability and surfactant-generated microcell structuralstrength. In order to control the amount and rate of cross-linking, itmay be desired to control the pH of the mixed components. For example,in acidic conditions (pH˜4.0), the cross-linking will occur very quicklyand the mixture will have a short pot-life. At higher pH (˜10.0), thecross-linking proceeds more slowly and may be controlled by heat. Thecross-linking component may increase the rate at which gel formationoccurs and allow for gel formation to occur at a lower temperature. Inaddition, the cross-linking component may improve the strength of thecomposite material.

[0041] The first layer of the composite material of the presentinvention may also comprise resin which may provide a polymer shell toencapsulate air. In one embodiment, the resin is DPG-38, available fromParachem of Dalton, Ga.

[0042] The first layer of the composite materials of the presentinvention has “bounce back” characteristics due to gel formation. In oneembodiment, the “bounce back” characteristics may be further enhancedthrough the use of additional components. As used herein, “bounce back”refers to the ability of the material to return to its original shapeafter having been distorted, such as stretched or compressed. Theadditional components may coat the inside of the microcell such that themicrocell reverts to its original shape after having been distorted.Preferred components useful for achieving bounce back characteristicsinclude CTO101 (silicon oil; Kelman Industries, Duncan, S.C.), Freepel1225 (BF Goodrich, Cleveland, Ohio), Sequapel 409 (Omnovasolutions, Inc.of Chester, S.C.), Michem emulsion 41740 (available from Michelman, Inc.of Cincinnati, Ohio), Syloff-1171A (available from Dow Corning,Corporation of Midland, Mich.), Syloff-62 (Dow Corning), Syloff-7910(Dow Corning) and Aurapel 391 (available from Sybron/Tanatex of Norwich,Conn.). These components also ensure that the microcells do notaggregate and form clumps of microcells.

[0043] As noted, the first layer of the composite materials of thepresent invention comprising a binder component, a surfactant componentand a gel catalyst component may further comprise a filler component.The filler component of the present invention preferably includes clay.The clay is preferably China clay which is very soft and light. Inaddition, the clay may be Paragon™, which is a soft clay (i.e. it issoft to the touch), Suprex™, which is a hard clay (i.e. it is hard tothe touch), Suprex™ amino silane treated clay, which is used forcrosslinking, because it will chemically bond with binder, and forhighloading, BallclayT™, which has elastic properties (i.e. it feelsrubbery), Texwhite 185 (available from Huber, Dry Branch, Ga.), and ECC1201 (available from Huber). All of above-listed clay products, unlessotherwise noted, are available, for example, from Kentucky-TennesseeClay Company of Langley, S.C. In one embodiment, the clay is Ballclay™3380 which is particularly inexpensive compared to other clays. In apreferred embodiment, the clay is Kaolin clay which is a lower gradeChina clay. In particularly preferred embodiments, the clay is Texwhite185 and/or ECC 1201.

[0044] In the present invention, clay is a preferred filler because ofits elongation properties (it has a low modulus), its abrasionresistance, its tear resistance, and its tensile strength. Moreover,clay is a good heat barrier; it does not disintegrate when an open flame(temperature ≧1500° F.) is applied directly to a first layer of thepresent invention that includes clay. In addition, clay provides aslick, elastic, glassy surface which exhibits flexibility. Furthermore,as noted, clay is inexpensive and thus can provide a low cost fabricmaterial.

[0045] The filler material may alternatively or additionally comprise afiller selected from the group consisting of decabromodiphenyloxide(FRD-004; Tiarco Chemicals,. Dalton, Ga.), antimony trioxide, calciumcarbonate, charged calcium carbonate, titanium dioxide, fly ash (such asAlsil O4TR™ class F fly ash produced by JTM Industries, Inc. of MartinLake and Jewett, Tex. which has a particle size such that less than 0.03% remains on an agitated 0.1 inch X 0.1 inch screen), 3-X mineralitemica (available from Engelhard, Inc. of Louisville, Ky.) and glass orceramic microspheres (glass microspheres are 2.5 times lighter thanceramic microspheres and also provide fire resistance), or any mixtureof these filler materials to meet desired cost and weight criteria.Glass and ceramic microspheres are manufactured by Zeelan Industries of3M Center Bldg., 220-8E-04, St. Paul, Minn. 55144-1000. Calciumcarbonate may be obtained from Franklin Industrial Minerals of 612 TenthAvenue North, Nashville, Tenn. 37203.

[0046] Calcium carbonate, talc and fly ash filler increase the weight ofthe product, but utilization of glass and/or ceramic microspheresenables the manufacture of a product with reduced weight and increasedfire resistant properties. Clay may impart to the product the followingnonlimiting characteristics: (1) lower heat build-up, (2) heatreflectance properties, (3) fire barrier properties, (4) no weight losswhen exposed to heat and open flame, and (5) reduced disintegration whenexposed to heat and open flame. Decabromodiphenyloxide and antimonytrioxide impart the following nonlimiting characteristics: (1) flameretardant properties, (2) capability of forming a char, and (3)capability of stopping the spread of flames. It is believed that the gasproduced from the heating of the decabromodiphenyloxide can also act asa flame retardant because the gas uses up oxygen or depletes oxygen inthe layer next to the fabric and suppresses or stops the fire fromfurther progression.

[0047] Glass and ceramic microspheres can withstand heat greater than2000° F. Also, glass and ceramic microspheres increase compressivestrength, absorb no latex and/or water and thus permit the faster dryingof the product. Glass and ceramic microspheres also increase productflexibility.

[0048] Further, the glass and ceramic microspheres help to increase thepot life of the first layer. Heavier particles in the fillers, althoughthey may comprise but a small percentage of the particles in the filler,have a tendency to settle near the bottom of a storage vessel. Whenglass and/or ceramic microspheres are mixed together with anotherfiller, a dispersion is produced which has an increased pot life orshelf life. Without wishing to be bound by any particular theory, it isbelieved that as the filler particles naturally fall in the vessel andthe glass and ceramic microspheres rise, the smaller size fillerparticles are supported by the glass and/or ceramic microspheres, thusenabling the microspheres to stay in solution and preventing the fillerparticles, to at least some extent, from descending to the bottom of thevessel.

[0049] The substrate of the present invention may be any suitablereinforcement material capable of withstanding processing temperatures,such as glass fibers, polyester fibers, cellulosic fibers, asbestos,steel fibers, alumina fibers, ceramic fibers, nylon fibers, graphitefibers, wool fibers, boron fibers, carbon fibers, jute fibers,polyolefin fibers, polystyrene fibers, acrylic fibers,phenolformaldehyde resin fibers, aromatic and aliphatic polyamidefibers, polyacrylamide fibers, polyacrylimide fibers or mixtures thereofwhich may include bicomponent fibers. The substrate provides strengthfor the composite material.

[0050] Examples of substrates in accordance with the invention include,inter alia, glass, fiberglass, ceramics, graphite (carbon), PBI(polybenzimidazole), PTFE, polyaramides, such as KEVLAR198 and NOMEX™,metals including metal wire or mesh, polyolefins such as TYVEK™,polyesters such as DACRON™ or REEMAY™, polyamides, polyimides,thermoplastics such as KYNAR™ and TEFZEL™, polyether sulfones, polyetherimide, polyether ketones, novoloid phenolic fibers such as KYNOL™, KoSa™polyester fibers, JM-137 M glass fibers, Owens-Corning M glass,Owens-Corning K glass fibers, Owens-Corning H glass fibers, Evanite 413Mglass microfibers, Evanite 719 glass microfibers, cellulosic fibers,cotton, asbestos and other natural as well as synthetic fibers. Thesubstrate may comprise a yarn, filament, monofilament or other fibrousmaterial either as such or assembled as a textile, or any woven,non-woven, knitted, matted, felted, etc. material. The polyolefin may bepolyvinyl alcohol, polypropylene, polyethylene, polyvinyl chloride,polyurethane, etc. alone or in combination with one another. Theacrylics may be DYNEL, ACRILAN and/or ORLON. RHOPLEX AC-22 and RHOPLEXAC-507 are acrylic resins sold by Rohm and Haas which also may be used.The cellulosic fibers may be natural cellulose such as wood pulp,newsprint, Kraft pulp and cotton and/or chemically processed cellulosesuch as rayon and/or lyocell.

[0051] Examples of woven materials that may be useful in the presentinvention include continuous fiberglass veils, such as Pearlveil™ 110,Pearlveil™ 210, Curveil™ 120, Curveil™ 220, Flexiveil™ 130, Flexiveil™230 and Pultrudable veil (all available from Schmelzer Industries, Inc.,Somerset, Ohio). The non-woven materials may be Airlaid (PrecisionFabrics Group, North Carolina) and Spunbond (Freudenberg Non-Woven,North Carolina). Nonlimiting examples of filament materials include C,DE, G, H, K, M filaments (glass fiber filaments of differingthicknesses) of various grades, including electrical grade, chemicalgrade and high strength grade (all available from BFG Industries, Inc.of Greensboro, N.C.). As used herein, a fiberglass mat includes nonwovenand woven fiberglass mats. In one embodiment, the fiberglass mat is anon-woven mat which comprises from about 70-95% H glass filaments, fromabout 0-5% Evanite microglass at 4.5 microns, from about 0-15% polyesterfiber (50/50 mix of ¼ inch and {fraction (1/2)} inch length), and fromabout 5-10% acrylic based binder with a glass transition temperature(Tg) at 18° F.

[0052] In a particularly preferred embodiment, the substrate of thepresent invention is a woven fiberglass mat such as style 1625, style1610 and style 1614 of BGF Industries (Greensboro, N.C.).

[0053] The composite materials of the present invention may be employedto make heat insulating, fire resistant building materials. Suchbuilding materials may be prepared during the building materials makingprocess to include the composite materials of the present invention, orthe composite materials may be utilized after building materials havealready been installed. The composite materials may be used on their ownor in conjunction with (e.g. as a liner for) other materials. Forexample, they may be applied to a structural article, such as buildingmaterials (e.g. gypsum board and siding materials, including sheathing)to obtain a heat insulating, fire resistant structural article. Such astructural article is useful for providing effective fire walls inbuildings, including homes, and can provide a greater escape time andreduced heat exposure for the occupants of the building. In addition,the composite materials of the present invention may be applied to atticceilings. The composite materials may be used to surface a roof prior tothe application of roofing materials, or they may comprise part of aroofing material.

[0054] The composite materials may further be used to impart heatinsulation and fire resistance to other objects, such as motor vehicles,trains, aircrafts, space ships, heating units, air conditioners, washingmachines, dryers, furniture, mattresses and any other objects for whichheat insulating and fire resistance properties are desired, such asupholstered articles, bedroom articles, (including children's bedroomarticles), draperies, carpets, tents, awnings, fire shelters, sleepingbags, ironing board covers, barbecue grill covers, fire resistantgloves, airplane seats, engine liners, and fire-resistant clothing forrace car drivers, fire fighters, jet fighter pilots, astronauts, facingsheets, building air duct liners, roofing underlayment (or roofingfelt), underlayment for organic, built up roofing materials, rollroofing, modified roll products, filter media (including automotivefilters), automotive hood liners, head liners, fire walls, vaporbarriers etc. The use of the composite materials of the presentinvention in articles may enable the articles to exceed currentflammability standards.

[0055] Composite materials made in accordance with this invention may beof any shape. Preferably, such articles are planar in shape. Thecomposite materials of the present invention are flexible and pliable.In addition they are durable and preferably do not crack upon bending.

[0056] In making the composite material, a planar substrate may becoated on one side or both sides depending on the intended application.As used herein, “coated on one side or both sides” means that thecoating coats at least a part of one side or at least a part of bothsides of the substrate. For instance, if one side of the substrate iscoated with the filler/binder coating, the other surface may be coatedwith another material. In the roofing materials industry, for example,the other material may be conventional roofing asphalt, modifiedasphalts and non-asphaltic coatings, and the article may then be toppedwith roofing granules. It is believed that such roofing material couldbe lighter in weight, offer better fire resistance and betterperformance characteristics (such as cold weather flexibility,dimensional stability and strength) than prior art roofing materials.

[0057] Additionally, the composite material may be coated with a waterrepellent material or the water repellant material may be added in thecoating (i.e. internal water proofing). Two such water repellantmaterials are Aurapel™ 330R and Aurapel™ available from Sybron/Tanatexof Norwich, Conn. In addition, Omnova Sequapel™ and Sequapel 417(available from Omnovasolutions, Inc. of Chester, S.C.); BS-1306, BS-15and BS-29A (available from Wacker of Adrian, Mich.); Syl-ff™-7922,Syl-off™-1171A, Syl-off™—7910 and Dow Corning 346 Emulsion (availablefrom Dow Corning, Corporation of Midland, Mich.); Freepel™-1225(available from BFG Industries of Charlotte, N.C.); and Michem™Emulsion-41740 and Michem™ Emulsion-03230 (available from Michelman,Inc. of Cincinnati, Ohio) may also be used. It is believed that waxemulsions, oil emulsions, silicone emulsions, polyolefin emulsions andsulfonyls as well as other similar performing products may also besuitable water repellant materials.

[0058] A defoamer may also be added to the coating of the presentinvention to reduce and/or eliminate foaming during production. One suchdefoamer is Drew Plus Y-250 available from Drews Inductrial Division ofBoonton, N.J. In addition, ionic materials may be added to increase theionic charge of the coating, such as ammonium hydroxide, Natrosol-NEC™available from Hercules of Wilmington, Del.) and ASE-95NP and ASE-60(available from Rohm & Haas of Charlotte, N.C.).

[0059] Fire retardant materials may also be added to the first layer ofthe composite materials of the present invention to further improve thefire resistance characteristics. Nonlimiting examples of fire retardantmaterials which may be used in accordance with the present inventioninclude FRD-004 (decabromodiphenyloxide; Tiarco Chemiclas, Dalton, Ga.),FRD-01, FR-10, FR-11, FR-12, FR-13, FR-14 (all available from TiarcoChemicals), zinc oxide, and aluminum trihydrate (ATH).

[0060] Further, heat insulating and fire resistant composite materialsmade in accordance with the invention may be coated with an algaecidesuch as zinc powder, copper oxide powder or the herbicides Atrazineavailable from e.g. Ribelin Inductries or Diuron avaibable from e.g.Olin Corporation, and antifungal material such as Micro-Chek™ 11P, anantibacterial material such as Micro-Check™ 11-S-160, a surface frictionagent such as Byk™-375, a flame retardant material such as ATH (aluminumtrihydrate) available from e.g. Akzo Chemicals and antimony trioxideavailable from e.g. Laurel Inductries. In addition, color pigments,including, but not limited to, T-113 (Abco, Inc.), W-4123 Blue Pigment,W2090 Orange Pigment, W7717 Black Pigment and W6013 Green Pigment, ironoxide red pigments (available from Engelhard of Louisville, Ky.) mayalso be added to the coating of the present invention to impact desiredcharacteristics, such as a desired color. The Micro-Chek™ products areavailable from the Ferro Corporation of Walton Hills, Ohio. Byk-375 maybe obtained from Wacker Silicone Corporation of Adrian, Mich. andT-1133A is sold by Abco Enterprises Inc. of Allegan, Mich.

[0061] The additional coatings of e.g. water repellant material,antifungal material, antibacterial material, etc., may be applied to oneor both sides of composite materials otherwise having filler/bindercoating on one of both sides of the substrate. For example, heatinsulating, fire resistant composite materials comprising substratescoated on one or both sides with filer/binder coatings could be coatedon one side with a water repellant composition and on the other sidewith an antibacterial agent. Alternatively, the water repellantmaterial, antifungal material, antibacterial material, etc., may beadded to the coating before it is used to coat the substrate.

[0062] As indicated, the heat insulating, fire resistant compositestructural material of the present invention is useful in themanufacture of mattresses, particularly mattress borders. In mattressborder embodiments, the composite structural material is placed eitherdirectly beneath the outer ticking layer or beneath a foam layer(preferably ¼″ polyurethane foam) that is itself beneath the tickinglayer. In this embodiment, the composite material may be used to line adecorative mattress fabric to produce a heat insulating, fire resistantmattress fabric. Nonlimiting examples of mattress fabrics includeticking (known in the art as a strong, tightly woven fabric comprisingcotton or linen and used especially to make mattresses and pillowcovering), or fabrics comprising fibers selected from the groupconsisting of cotton, polyester, rayon, polypropylene, and combinationsthereof. The lining may be achieved by methods known in the art. Forexample, the composite material of the present invention may simply beplaced under a mattress fabric. Or, the heat insulating, fire resistantcomposite material may be bonded or adhered to the mattress fabric, forexample using a flexible and preferably nonflammable glue or stitchedwith fire resistant thread i.e., similar to a lining, to make a heatinsulating, fire resistant mattress fabric. The fire resistant mattressfabric of the present invention may then be used by the skilled artisanto manufacture a mattress product which has improved flammabilitycharacteristics.

[0063] Further materials which may be incorporated into the mattressproducts, particularly mattress borders, include construction materials,such as non fire retardant or fire retardant thread for stitching themattress materials together (e.g. glass thread or Kevlar thread) andnon-fire retardant or fire retardant tape. Silicon may be used withKevlar thread to diminish breakage and enhance production time.

[0064] Fire resistant composite materials made in accordance with thepresent invention may be used in conjunction with foamed heat insulatingmaterials made by any of the known methods for making foamedcompositions such as, for example, aeration by mechanical mixing and theother techniques described in U.S. Pat. No. 5,110,839.

[0065] The composite materials of the present invention may be used toproduce materials with characteristics similar to foam and cushionlayers used in mattresses and may replace or be added in addition tosuch layers. In such embodiments, the foam and cushioning layers madewith the composite materials of the present invention impart heatinsulation and fire resistance characteristics to the mattress when usedtherein. The composite materials also impart heat insulation and fireresistance to other products when used therein.

[0066] Table I below provides, in approximate percentages, thecomponents of the first layer that the applicants believe would beuseful in exemplary embodiments of composite material of the presentinvention. Although the table shows possible combinations of binder,filler and surfactant, it is believed that other combinations may beemployed. TABLE 1 Coating Components 1 2 3 4 5 6 7 8 BINDER Rovene 440236.25 26.73 18.71 18.71 18.71 18.71 36.25 36.25 Rhoplex 3349 36.25 26.7318.71 18.71 18.71 18.71 36.25 36.25 SURFACTANT Stanfax 320 4.5 3.32 2.302.30 2.30 2.30 2.30 2.30 FILLER Clay Type? 30.0 JTM Fly Ash Calcium Car-30.0 bonate Z-light Micro- 30.0 7.5 3.75 spheres GEL CATALYST SSF-GEL13.0 13.0 11.7 11.7 8.8 8.8 8.8 8.8 MISCELLANEOUS TiO₂ 30.0 7.5 FR-1526.27 26.27 26.27 26.27 26.27 26.27 26.27 DPG-38 5.0 3.69 3.5 3.5 3.53.5 3.5 3.5 UP-750 5.0 3.69 3.5 3.5 3.5 3.5 3.5 3.5

[0067] The heat insulating, fire resistant composite materials, asmentioned, may include a substrate. The first layer of the compositematerial comprises approximately 34% by weight of the heat insulating,fire resistant composite material. In the first layer, about 10% toabout 55% by weight is binder, about 2% to about 15% is surfactant, fromabout 5% to about 20% gel catalyst, and from about 0% to about 55% isfiller. In a preferred embodiment, the first layer comprises about 42%binder, about 5% surfactant, about 13% gel catalyst and about 30%filler. This is wet weight and the remainder is water. The filler ispreferably about 30% clay. The second layer is preferably aluminum foiland is approximately 0.5% to 1.5% by weight of the composite material,depending on whether one or two layers of foil are employed. Thesubstrate is preferably woven glass. The binder which bonds together theglass fibers is approximately about 25% to about 55% Rhoplex 3349 and/orRovene 4402, or any other suitable binder. Nonlimiting examples ofsuitable binders are provided herein above.

[0068] The substrate may be coated with the first layer by air spraying,dip coating, knife coating, roll coating or film application such aslamination/heat pressing. The first layer may be bonded to the substrateby chemical bonding, mechanical bonding and/or thermal bonding.Mechanical bonding is achieved by force feeding the first layer onto thesubstrate with a knife. The second layer which comprises the metalliccomponent may be adhered to the first layer by any means known in theart, including chemical bonding (e.g. with adhesives), mechanicalbonding (e.g. by adding the metallic component to the first layer whileit is still wet and drying the first layer thereafter), by electrodeposition, spraying, coating with a knife, etc.

[0069] Heat insulating, fire resistant structural materials andcomposite materials made in accordance with this invention may be of anyshape. Preferably, such articles are planar in shape.

[0070] When a substrate is employed, the first layer may be adhered onone side or both sides of the substrate depending on the intendedapplication. For instance, if one side of the susbtrate is covered atleast to some extent with the first layer (and the second layercomprising the metallic component), then the other surface may becovered to at least some extent with another material. In the roofingmaterials industry, for example, the other material may be conventionalroofing asphalt, modified asphalts and non-asphaltic coatings, and thearticle can then be topped with roofing granules. It is believed thatsuch roofing material could be lighter in weight, offer better fireresistance and better performance characteristics (such as cold weatherflexibility, dimensional stability and strength) than prior art roofingmaterials.

[0071] The mixture comprising the binder, surfactant and filler may havea consistency of a light foam, such as shaving cream. It is believedthat due to the low density of the mixture, the surfactant-generatedmicrocells formed therein do not pass through the substrate when appliedthereto. If desired, in order to ensure that the mixture does not bleedthrough the substrate, the viscosity of the first layer may be increasedthrough mixing. Nonlimiting examples of thickening agents includeAcrysol ASE-95NP, Acrysol ASE-60, Acrysol ASE-1000, Rhoplex ASE-75,Rhoplex ASE-108NP, and Rhoplex E-1961, all available from Rohm & Haas.

[0072] Additionally, the composite material may be coated with a waterrepellent material or the water repellent material may be added in thefirst layer (i.e., internal water proofing). Two such water repellentmaterials are Aurapel™ 330R and Aurapel™ 391 available fromSybron/Tanatex of Norwich, Conn. In addition, Omnova Sequapel™ andSequapel 417 (available from Omnovasolutions, Inc. of Chester, S.C.);BS-1306, BS-15 and BS-29A (available from Wacker of Adrian, Mich.);Syl-off™-7922, Syl-off™-1171A, Syl-off™—7910 and Dow Corning 346Emulsion (available from Dow Corning, Corporation of Midland, Mich.);Freepel™ -1225 (available from BFG Industries of Charlotte, N.C.); andMichem Emulsion-41740 and Michem Emulsion™ 03230 (available fromMichelman, Inc. of Cincinnati, Ohio) may also be used. It is believedthat wax emulsions, oil emulsions, silicone emulsions, polyolefinemulsions and sulfonyls as well as other similar performing products mayalso be suitable water repellent materials. These materials are alsouseful, as mentioned above, for imparting bounce back characteristics tothe composite material of the invention. Water repellents may beparticularly preferred for example, in the manufacture of buildingmaterials, crib mattresses, airplane seats and in the manufacture offurniture, particularly for industrial use.

[0073] A defoamer may also be added to the first layer of the presentinvention to reduce and/or eliminate foaming during production. One suchdefoamer is Y-250 available from Drews Industrial Division of Boonton,N.J.

[0074] Fire retardant materials may also be added to the compositematerials, and particularly to the first layer of the present inventionto further improve the fire resistance characteristics. Nonlimitingexamples of fire retardant materials which may be used in accordancewith the present invention include FRD-004 (decabromodiphenyloxide;Tiarco Chemicals, Dalton, Ga.), FRD-01, FR-10, FR-11, FR-12, FR-13,FR-14, FR-15 (all available from Tiarco Chemicals) zinc oxide, andaluminum trihydrate (ATH).

[0075] In addition, color pigments, including, but not limited to, T-113(Abco, Inc.), W-4123 Blue Pigment, W2090 Orange Pigment, W7717 BlackPigment and W6013 Green Pigment, iron oxide red pigments (available fromEngelhard of Louisville, Ky.) may also be added to the first layer ofthe present invention to impart desired color characteristics.

[0076] The additional coatings of, e.g. water repellent material,antifungal material, antibacterial material, etc., may be applied to oneor both sides of the composite materials. For example, compositematerials comprising substrates including on one or both sides thefiller/surfactant/binder first layer could further include a waterrepellant on one side an antibacterial agent on the other side.Alternatively, the water repellent material, antifungal material,antibacterial material, etc., may be added to the first layer before itis adhered to the substrate.

[0077] Although the present invention has been described with referenceto certain preferred embodiments, various modifications, alterations,and substitutions will be apparent to those skilled in the art withoutdeparting from the spirit and scope of the invention, as defined by theappended claims. For example, other sources of filler as well asmixtures of acrylic latex and/or surfactants may be used in formulatingthe fire resistant fabric materials of the present invention. Moreover,the first layer may be applied to various types of substrates, asdescribed above.

What is claimed is:
 1. A composite material comprising: (a) a firstlayer which comprises a surfactant component, surfactant-generatedmicrocells, a gel catalyst component and a binder component; and (b) asecond layer comprising a metallic component adhered to the first layer.2. A composite material comprising (a) a substrate; (b) a first layeradhered to the substrate to provide a coated substrate, said first layercomprising a surfactant component, surfactant-generated microcells, agel catalyst component and a binder component; and (c) a second layercomprising a metallic component adhered to the coated substrate.
 3. Thecomposite material according to claims 1 or 2 wherein the first layerfurther comprises a filler component.
 4. The composite materialaccording to claim 2 wherein said substrate is planar and said firstlayer is adhered to one side of the substrate.
 5. The composite materialaccording to claim 2 wherein said substrate is planar and said firstlayer is adhered to both sides of the substrate.
 6. The compositeaccording to claims 4 or 5 wherein said second layer is adhered to oneside of said coated substrate.
 7. The composite according to claims 4 or5 wherein said second layer is adhered to both sides of said coatedsubstrate
 8. The composite material according to claims 1 or 2 furthercomprising a water repellant material.
 9. The composite materialaccording to claims 1 or 2 further comprising an antifungal material.10. The composite material according to claims 1 or 2 further comprisingan antibacterial material.
 11. The composite material according toclaims 1 or 2 further comprising a surface friction agent.
 12. Thecomposite material according to claims 1 or 2 further comprising a flameretardant material.
 13. The composite material according to claims 1 or2 further comprising an algaecide.
 14. The composite material accordingto claims 1 or 2 further comprising a dye.
 15. The composite materialaccording to claims 1 or 2, wherein the metallic component is selectedfrom the group consisting of aluminum or stainless steel.
 16. Thecomposite material according to claim 15 wherein the metallic componentis aluminum foil.
 17. The composite material according to claim 3wherein the filler comprises clay.